ALTERNATING CURRENT DIELECTROPHORESIS OF CORE-SHELL NANOPARTICLES: EXPERIMENTS AND COMPARISON WITH THEORY

Nanoparticles are fascinating where physical and optical properties are related to size. Highly controllable synthesis methods and nanoparticle assembly are essential [6] for highly innovative technological applications. Among nanoparticles, nonhomogeneous core-shell nanoparticles (CSnp) have new properties that arise when varying the relative dimensions of the core and the shell. This CSnp structure enables various optical resonances, and engineered energy barriers, in addition to the high charge to surface ratio. Assembly of homogeneous nanoparticles into functional structures has become ubiquitous in biosensors (i.e. optical labeling) [7, 8], nanocoatings [9-13], and electrical circuits [14, 15]. Limited nonhomogenous nanoparticle assembly has only been explored. Many conventional nanoparticle assembly methods exist, but this work explores dielectrophoresis (DEP) as a new method. DEP is particle polarization via non-uniform electric fields while suspended in conductive fluids. Most prior DEP efforts involve microscale particles. Prior work on core-shell nanoparticle assemblies and separately, nanoparticle characterizations with dielectrophoresis and electrorotation [2-5], did not systematically explore particle size, dielectric properties (permittivity and electrical conductivity), shell thickness, particle concentration, medium conductivity, and frequency. This work is the first, to the best of our knowledge, to systematically examine these dielectrophoretic properties for core-shell nanoparticles. Further, we conduct a parametric fitting to traditional core-shell models. These biocompatible core-shell nanoparticles were studied to fill a knowledge gap in the DEP field. Experimental results (chapter 5) first examine medium conductivity, size and shell material dependencies of dielectrophoretic behaviors of spherical CSnp into 2D and 3D particle-assemblies. Chitosan (amino sugar) and poly-L-lysine (amino acid, PLL) CSnp shell materials were custom synthesized around a hollow (gas) core by utilizing a phospholipid micelle around a volatile fluid templating for the shell material; this approach proves to be novel and distinct from conventional core-shell models wherein a conductive core is coated with an insulative shell. Experiments were conducted within a 100 nl chamber housing 100 um wide Ti/Au quadrapole electrodes spaced 25 um apart. Frequencies from 100kHz to 80MHz at fixed local field of 5Vpp were tested with 10-5 and 10-3 S/m medium conductivities for 25 seconds. Dielectrophoretic responses of ~220 and 340(or ~400) nm chitosan or PLL CSnp were compiled as a function of medium conductivity, size and shell material.

Synthesis of novel solid materials from carbon dioxide and carbon monoxide

The increase of atmospheric CO2 has been identified as the primary cause for the observed global warming over the past century. The geological and oceanic sequestration of CO2 has issues, such as cost and leakage as well as effects on sea biota. The ideal solution should be the conversion of CO2 into useful materials. However, most processes require high energy input. Therefore, it is necessary to explore novel processes with low energy demands to convert CO2 to useful solid materials. Amorphous carbon nitride and graphone received much attention due to their unusual structures and properties as well as their potential applications. However, to date there has been no attempt to synthesize those solid materials from CO2. Lithium nitride (Li3N) and lithium imide (Li2NH) are important hydrogen storage materials. However, their optical properties and reactivity has not yet studied. This dissertation research is aimed at the synthesis of carbon nitrides and graphone from CO2 and CO via their reaction with Li3N and Li2NH. The research was focused on (1) the evaluation of Li3N and Li2NH properties, (2) thermodynamic analysis of conversion of carbon dioxide and carbon monoxide into carbon nitride and other solid materials, (3) synthesis of carbon nitride from carbon dioxide, and (4) synthesis of graphone from carbon monoxide. First, the properties of Li3N, Li2NH, and LiNH2 were investigated. The X-ray diffraction measurements revealed that heat-treatment at 500°C introduce a phase transformation of β-Li3N to α-Li3N. Furthermore, the UV-visible absorption evaluation showed that the energy gaps of α-Li3N and β-Li3N are 1.81 and 2.14 eV, respectively. The UV-visible absorption measurements also revealed that energy gaps are 3.92 eV for Li2NH and 3.93 eV for LiNH2. This thermodynamic analysis was performed to predict the reactions. It was demonstrated that the reaction between carbon dioxide and lithium nitride is thermodynamically favorable and exothermic, which can generate carbon nitride and lithium cyanamide. Furthermore, the thermodynamic calculation indicated that the reaction between carbon monoxide and lithium imide can produce graphone and lithium cyanamide along with releasing heat. Based on the above thermodynamic analysis, the experiment of CO2 and Li3N reaction and CO and Li2NH were carried out. It was found that the reaction between CO2 and Li3N is very fast and exothermic. The XRD and element analysis revealed that the products are crystal lithium cyanamide and amorphous carbon nitrides with Li2O and Li2CO3. Furthermore, TEM images showed that carbon nitrides possess layer-structure, namely, it is graphene-structured carbon nitride. It was found that the reaction between Li2NH and CO was also exothermic, which produced graphone instead of carbon nitride. The composition and structures of graphone were evaluated by XRD, element analysis, TEM observation, and Raman spectra.

Fabrication of nanoparticles by short-distance sputter deposition

During the past decades, tremendous research interests have been attracted to investigate nanoparticles due to their promising catalytic, magnetic, and optical properties. In this thesis, two novel methods of nanoparticle fabrication were introduced and the basic formation mechanisms were studied. Metal nanoparticles and polyurethane nanoparticles were separately fabricated by a short-distance sputter deposition technique and a reactive ion etching process. First, a sputter deposition method with a very short target-substrate distance is found to be able to generate metal nanoparticles on the glass substrate inside a RIE chamber. The distribution and morphology of nanoparticles are affected by the distance, the ion concentration and the process time. Densely-distributed nanoparticles of various compositions are deposited on the substrate surface when the target-substrate distance is smaller than 130mm. It is much less than the atoms’ mean free path, which is the threshold in previous research for nanoparticles’ formation. Island structures are formed when the distance is increased to 510mm, indicating the tendency to form continuous thin film. The trend is different from previously-reported sputtering method for nanoparticle fabrication, where longer distance between the target and the substrate facilitates the formation of nanoparticle. A mechanism based on the seeding effect of the substrate is proposed to interpret the experimental results. Secondly, in polyurethane nanoparticles’ fabrication, a mechanism is put forward based on the microphase separation phenomenon in block copolymer thin film. The synthesized polymers have formed dispersed and continuous phases because of the different properties between segments. With harder mechanical property, the dispersed phase is remained after RIE process while the continuous phase is etched away, leading to the formation of nanoparticles on the substrate. The nanoparticles distribution is found to be affected by the heating effect, the process time and the plasma power. Superhydrophilic property is found on samples with these two types of nanoparticles. The relationship between the nanostructure and the hydrophilicity is studied for further potential applications.

Multimetallic complexes based on phosphine- and phosphine oxide- appended p-hydroquinones

Presented here, is the work done with a series of binucleating ligands based on phosphine and phosphine oxide appended p-hydroquinones and their reactions towards various metals sources. The long term goal of the project was to produce coordination polymers that would have novel electronic, magnetic, and optical properties which would be of use in the field of molecular electronics. Binucleating ligands contained a p-hydroquinone motif in which various phosphine- and phosphine oxide substituents have been placed in the ortho position relative to each of the hydroxy position were synthesized. A previously published synthetic method for such lugands utilized n-BuLi to form a phenyl lithium intermediate which was quenched with chlorodiphenylphosphine. This technique was also used to produce a ligand with diisopropylphosphine groups. Phosphine ligands, containing the same structural motif, were also generated using LDA as the lithiating agent. This technique was found to be higher yielding. Phosphine chalcogenide ligands were accessed by further oxidizing the low valent phosphorous centers with either hydrogen peroxide or with elemental sulfur. These ligands were characterized using multinuclear NMR, low and high resolution mass spectroscopy, FTIR, and single crystal X-ray diffraction. Their electrochemical properties were explored with cyclic voltammetry. The phosphine appended ligands were used in the synthesis of a several bimetallic complexes. It was found that the ligands readily reacted with NiCp2 and NiCp*2, displacing one of the cyclopentadiene (Cp) or pentamethylcyclopentadiene (Cp*) rings. A cyclopentadiene complexes, containing diisopropylphine, was readily oxidized by[FeCp2]PF6 to give a NMR silent mixed valence complex. Cyclic voltammetry of these complexes showed a number of reversible waves with a large potential separation. The mixed valence compounds also showed a large absorbance band in the NIR region which was assigned to be an intervalence charge transfer. The cyclic voltammetry and NIR spectroscopy suggest that these systems are very capable of efficient metal-to-metal charge transfer. These complexes were characterized by multinuclear NMR, single crystal X-ray diffraction, UV/VIS-NIR spectroscopy and elemental analysis. The phosphine oxide ligands were reacted with a variety of different metal sources but limited success was gained in obtaining single crystals, allowing structural characterization of these compounds. Single crystals were obtained from products generated by reacting the diphenylphosphine oxide ligand with (Bipy)Cu(NO3)2 and Cu(NO3)2. In all cases the ligand had been further oxidized to a 2,5-dihydroxy-1,4-benzoquinone motif. In the reaction between the diphenylphosphine oxide ligand and (Bipy)Cu(NO3)2 it was found that the phosphine oxide moiety was involved with intermolecular coordination leading to the formation of a one-dimensional polymer composed of a series of bimetallic complexes tethered together. When NaSbF6 was present in the reaction with (Bipy)Cu(NO3)2 a unique tetrametallic complex was formed. Here the phospine oxide moiety was oriented so that two bimetallic complexes were bound together. If only Cu(NO3)2 was present, a two-dimensional polymeric sheet was formed where the ligand was present in two different coordination modes. The electronic properties of these complexes remained to be assessed.

Negative index metamaterials and metaspacers for optical frequencies

Metamaterials are artificial materials that exhibit properties, such as negative index of refraction, that are not possible through natural materials. Due to many potential applications of negative index metamaterials, significant progress in the field has been observed in the last decade. However, achieving negative index at visible frequencies is a challenging task. Generally, fishnet metamaterials are considered as a possible route to achieve negative index in the visible spectrum. However, so far no metamaterial has been demonstrated to exhibit simultaneously negative permittivity and permeability (double-negative) beyond the red region of the visible spectrum. This study is mainly focused on achieving higher operating frequency for low-loss, double-negative metamaterials. Two double-negative metamaterials have been proposed to operate at highest reported frequencies. The first proposed metamaterial is based on the interaction of surface plasmon polaritons of a thin metal film with localized surface plasmons of a metallic array placed close to the thin film. It is demonstrated that the metamaterial can easily be scaled to operate at any frequency in the visible spectrum as well as possibly to the ultraviolet spectrum. Furthermore, the underlying physical phenomena and possible future extensions of the metamaterial are also investigated. The second proposed metamaterial is a modification to the so-called fishnet metamaterial. It has been demonstrated that this ‘modified fishnet’ exhibits two double-negative bands in the visible spectrum with highest operating frequency in the green region with considerably high figure of merit. In contrast to most of the fishnet metamaterials proposed in the past, behavior of this modified fishnet is independent of polarization of the incident field. In addition to the two negative index metamaterials proposed in this study, the use of metamaterial as a spacer, named as metaspacer, is also investigated. In contrast to naturally available dielectric spacers used in microfabrication, metaspacers can be realized with any (positive or negative) permittivity and permeability. As an example, the use of a negative index metaspacer in place of the dielectric layer in a fishnet metamaterial is investigated. It is shown that fishnet based on negative index metaspacer gives many improved optical properties over the conventional fishnet such as wider negative index band, higher figure of merit, higher optical transmission and stronger magnetic response. In addition to the improved properties, following interesting features were observed in the metaspacer based fishnet metamaterial. At the resonance frequency, the shape of the permeability curve was ‘inverted’ as compared to that for conventional fishnet metamaterial. Furthermore, dependence of the resonance frequency on the fishnet geometry was also reversed. Moreover, simultaneously negative group and phase velocities were observed in the low-loss region of the metaspacer based fishnet metamaterial. Due to interesting features observed using metaspacer, this study will open a new horizon for the metamaterial research.